Wu H F, Guan F Y, Luo Y
Institute of Pharmacology and Toxicology, Academy of Military Medical Sciences, Beijing 100850.
Yao Xue Xue Bao. 1997 May;32(5):377-83.
A systematic screening method has been developed for the detection of 29 central nervous system (CNS) drugs in human plasma, urine and gastric juice by high performance capillary electrophoresis (HPCE). The first step is sample preparation. The patient's or normal human plasma (0.5 ml) spiked with CNS drugs was extracted with 2 x 4 ml dichloromethane, while 2 ml of patient's or spiked urine was extracted with 2 x 6 ml chloroform. The combined extract from plasma or urine was evaporated to dryness in a rotation evaporator at 35 degrees C. The residue was dissolved in 100 microliters methanol and subsequently 400 microliters of redistilled water was added. The patient gastric juice (3 ml) was centrifuged at 2,000 r.min-1 for 5 min. The supernatant was filtered through 0.45 micron microporous membrane for injection onto capillary columns. The second step was to perform CZE separation in acidic buffer composed of 30 mmol.L-1(NH4)3PO4(pH 2.50) and 10% acetonitrile (condition A). Most of the benzodiazepines (diazepam, nitrazepam, chlordiazepoxide, flurazepam, extazolam, alprazolam) and methaqualone were baseline separated and detected at 5-13 min, while thiodiphenylamines showed group peaks at 3-5 min and barbiturates migrate with electroosmotic fluid (EOF) together. The third step is to separate the drugs in basic buffer constituted of 70 mmol.L-1 Na2HPO4(pH 8.60) and 30% acetonitrile (condition B). The thiodiphenylamines and some other basic drugs could be well separated, which include thihexyphenidyl, imipramine, amitriptyline, diphenhydramine, chlorpromazine, doxepin, chlorprothixene, promethazine and flurazepam, while the rest of the CNS drugs did not interfere with the separation. The last step was to separate the drugs by micellar electrokinetic chromatography (MEKC) in such a buffer as 70 mmol.L-1 SDS plus 15 mmol.L-1 Na2HPO4 (pH 7.55) and 5% methanol (condition C). Barbiturates (barbital, phenobarbital, methylphenobarbital, amobarbital, thiopental, pentobarbital, secobarbital) and some hydrophobic drugs (glutethimide, alprazolam, clonazepam, carbamazepine, trifluoperazine, oxazepam) could be well separated. These drugs might be identified by both the relative migration time (rtm = tdrug/tEOF) and the ratios of peak heights (rh) monitored at different wavelength, since the ratios are characteristic of the spectrum of a drug. This method has been used in several real clinical samples of intoxication. For example, perphenazine and doxepin were detected in the gastric juice and phenobarbital in blood and gastric juice of an intoxicated patient.
已开发出一种系统筛选方法,用于通过高效毛细管电泳(HPCE)检测人血浆、尿液和胃液中的29种中枢神经系统(CNS)药物。第一步是样品制备。向添加了中枢神经系统药物的患者或正常人血浆(0.5毫升)中加入2×4毫升二氯甲烷进行萃取,而2毫升患者或加标尿液则用2×6毫升氯仿萃取。血浆或尿液的合并萃取液在35℃的旋转蒸发仪中蒸发至干。残余物溶于100微升甲醇,随后加入400微升重蒸馏水。将患者胃液(3毫升)以2000转/分钟的速度离心5分钟。上清液通过0.45微米微孔膜过滤后注入毛细管柱。第二步是在由30毫摩尔/升(NH4)3PO4(pH 2.50)和10%乙腈组成的酸性缓冲液中进行毛细管区带电泳(CZE)分离(条件A)。大多数苯二氮䓬类药物(地西泮、硝西泮、氯氮卓、氟西泮、艾司唑仑、阿普唑仑)和甲喹酮在5至13分钟实现基线分离并被检测到,而硫二苯胺类药物在3至5分钟出现组峰,巴比妥类药物与电渗流(EOF)一起迁移。第三步是在由70毫摩尔/升Na2HPO4(pH 8.60)和30%乙腈组成的碱性缓冲液中分离药物(条件B)。硫二苯胺类药物和其他一些碱性药物能够得到很好的分离,其中包括甲磺酸苯扎托品、丙咪嗪、阿米替林、苯海拉明、氯丙嗪、多塞平、氯普噻吨、异丙嗪和氟西泮,而其余中枢神经系统药物不干扰分离。最后一步是在由70毫摩尔/升十二烷基硫酸钠加15毫摩尔/升Na2HPO4(pH 7.55)和5%甲醇组成的缓冲液中通过胶束电动毛细管色谱法(MEKC)分离药物(条件C)。巴比妥类药物(巴比妥、苯巴比妥、甲基苯巴比妥、异戊巴比妥、硫喷妥钠、戊巴比妥、司可巴比妥)和一些疏水性药物(格鲁米特、阿普唑仑、氯硝西泮、卡马西平、三氟拉嗪、奥沙西泮)能够得到很好的分离。这些药物可以通过相对迁移时间(rtm = tdrug/tEOF)以及在不同波长监测的峰高比(rh)来鉴定,因为这些比值是药物光谱的特征。该方法已应用于多个实际中毒临床样本。例如,在一名中毒患者的胃液中检测到了奋乃静和多塞平,在血液和胃液中检测到了苯巴比妥。